JPH0655815B2 - Method for producing arylene sulfide copolymer - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a novel arylene sulfide copolymer. More specifically, the present invention relates to various molded articles, films, fibers, or machine parts,
A method for producing an arylene sulfide copolymer having excellent heat resistance, mechanical properties, melt processability, and good transparency, which is suitable as a material for electric / electronic parts, etc. and has a slow crystallization rate Is.

[Prior Art] An arylene sulfide-based polymer having a structure in which an arylene group such as a phenylene group is linked via a thioether group includes a homopolymer and a copolymer, and as the former homopolymer, , For example structural formula Polyphenylene sulfide having is known as a typical one. This product is obtained, for example, by reacting dichlorobenzene with sodium sulfide (Japanese Patent Publication No. 52-12240). Such a homopolymer has high crystallinity, excellent chemical resistance, and excellent mechanical properties in a wide temperature range, and thus has excellent heat resistance. As an engineering plastic, it can be used as a mechanical component or electric / electronic component. It is preferably used for However, since the homopolymer has a high crystallization rate, it is poor in processability and has many problems when it is formed into a film, a fiber or the like.

On the other hand, although ordinary copolymers, especially random copolymers, generally have good melt processability, they have the drawback that they are difficult to crystallize and their heat resistance is significantly inferior to the above homopolymers.

Therefore, in order to improve the drawbacks of both, attempts have been made to develop a polymer obtained by copolymerizing various third components. For example A copolymer containing a bond such as
-41959, JP 61-283622, JP 61-2916
25 publication). However, these copolymers are not always sufficient in that they satisfy both crystallinity and melt processability.

On the other hand, a method in which dichlorobenzene isomers are used in combination for copolymerization has also been proposed (Japanese Patent Publication No. 52-12239 and Japanese Patent Publication No. 61-14228), but in this method, the heat resistance is not sufficient. There is a problem.

[Problems to be Solved by the Invention] Under the circumstances, an object of the present invention is that the crystallization rate is slow, the melt processability is good, and the heat resistance and mechanical properties are excellent. In addition, the object of the present invention is to provide a method for industrially advantageously producing an arylene sulfide copolymer having good transparency.

[Means for Solving Problems] The inventors of the present invention have conducted extensive studies to develop an arylene sulfide-based copolymer having the above-mentioned excellent characteristics, and as a result, have obtained a dihalogeno aromatic compound and an alkali metal as raw materials. It has been found that the object can be achieved by using a sulfide and a dihalogenoaromatic carboxylic acid or a salt thereof in a polar solvent, and the present invention has been completed based on this finding.

That is, the present invention is characterized in that (A) a dihalogeno aromatic compound, (B) an alkali metal sulfide, and (C) a dihalogeno aromatic carboxylic acid and / or an alkali metal salt thereof are contacted in a polar solvent. The present invention provides a method for producing an arylene sulfide copolymer.

Hereinafter, the present invention will be described in detail.

Examples of the polar solvent used in the method of the present invention include amide compounds, lactam compounds, urea compounds, cyclic organophosphorus compounds, and the like, specifically N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dipropylacetamide, N, N-dimethylbenzoic acid amide, caprolactam, N-methylcaprolactam, N-ethylcaprolactam, N-isopropylcaprolactam, N-isobutylcaprolactam, N-normalpropylcaprolactam, N-normal butyl caprolactam, N-cyclohexyl caprolactam, N-methyl-2
-Pyrrolidone, N-ethyl-2-pyrrolidone, N-isopropyl
-2-pyrrolidone, N-isobutyl-2-pyrrolidone, N-normal propyl-2-pyrrolidone, N-normal butyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N-methyl-3-methyl-2-pyrrolidone , N-cyclohexyl-2-pyrrolidone,
N-ethyl-3-methyl-2-pyrrolidone, N-methyl-3,4,5-trimethyl-2-pyrrolidone, N-methyl-2
-Piperidone, N-ethyl-2-piperidone, N-isopropyl-2-piperidone, N-methyl-6-methyl-2-
Piperidone, N-methyl-3-ethyl-2-piperidone, tetramethylurea, N, N'-dimethylethylenurea, N, N'-dimethylpropyleneurea, 1-methyl-1-oxosulfolane, 1-ethyl- 1-oxosulfolane, 1-phenyl-1-oxosulfolane, 1-methyl-1-oxophosphane, 1-normal-propyl-1-oxophosphane, 1-phenyl-1-oxophosphane and the like can be mentioned. These solvents may be used alone or in combination of two or more. Among the various polar solvents, N-alkyllactam and N-alkylpyrrolidone are preferable, and N-methylpyrrolidone is particularly preferable.

Examples of the dihalogeno aromatic compound used as the raw material component (A) in the method of the present invention include dihalogenobenzenes such as m-dihalobenzene and p-dihalobenzene, 2,3-dihalotoluene, 2,5-dihalotoluene, 2,6 -Dihalotoluene, 3,4-dihalotoluene, 2,5-dihaloxylene, 1-ethyl-2,5-dihalobenzene, 1,2,4,5-tetramethyl-3,6-dihalobenzene, 1-normalhexyl-2,5 -Dihalogenoalkyl- or cycloalkyl-substituted benzenes such as dihalobenzene, 1-cyclohexyl-2,5-dihalobenzene, 1-phenyl-2,5-dihalobenzene, -1benzyl-2,5-dihalobenzene, 1-p-toluyl- Dihalogenoaryl-substituted benzenes such as 2,5-dihalobenzene, 4,4'-
Examples thereof include dihalogenobiphenyls such as dihalophenyl, and dihalogenonaphthalenes such as 1,4-dihalonaphthalene, 1,6-dihalonaphthalene, and 2,6-dihalonaphthalene.

The two halogen elements in these dihalogeno aromatic compounds are respectively fluorine, chlorine, bromine or iodine, which may be the same or different from each other.

Among the above halogeno aromatic compounds, dihalobenzenes are preferable, and p-dichlorobenzene is particularly preferable.

In the method of the present invention, examples of the alkali metal sulfide used as the raw material component (B) include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, and cesium sulfide, which may be used alone. You may use it in combination of 2 or more type.

Among the above-mentioned alkali metal sulfides, lithium sulfide and sodium sulfide are preferable, and sodium sulfide is particularly preferable. Further, as the alkali metal sulfide, an anhydride, a hydrate, or an aqueous mixture can be used, but when using a hydrate or an aqueous mixture, a dehydration operation is performed before the reaction as described below. Need to do.

In the method of the present invention, a dihalogeno aromatic carboxylic acid and / or its alkali metal salt is used as the raw material component (C). Examples of the dihalogeno aromatic carboxylic acid and its alkali metal salt include those represented by the general formula (X ¹ and X ² in the formula are each a halogen atom,
They may be the same or different from each other, R is a hydrogen atom or an alkali metal, Y is a simple bond, —O—, —SO ₂ —, —S—, —CH ₂ —, — C (CH ₃ ) ₂ -or -C (CF
₃ ) _2- ) and the like.

Specific examples of the compound represented by the general formula (II) include 2,3-dihalobenzoic acid, 2,4-dihalobenzoic acid, 2,5-dihalobenzoic acid, 2,6-dihalobenzoic acid and 3, Examples thereof include 4-dihalobenzoic acid, 3,5-dihalobenzoic acid and alkali metal salts thereof. Further, specific examples of the compound represented by the general formula (III) include 4,4′-dihalobiphenyl.
-2-carboxylic acid, 4,4'-dihalobiphenyl-3-carboxylic acid, 3,4'-dihalobiphenyl- (2,4,5 or 6) -carboxylic acid, 2,4'-dihalobiphenyl -(3,4,5 or 6)-
Carboxylic acid, 3,4'-dihalobiphenyl- (2 ', 3',
5'or 6 ')-carboxylic acid, 2,4'-dihalobiphenyl- (2', 3 ', 5' or 6 ')-carboxylic acid, 2,3-
Dihalobiphenyl- (4,5 or 6) -carboxylic acid, 2,3 '
-Dihalobiphenyl- (2 ', 4', 5 'or 6')-carboxylic acid, 3,3'-dihalobiphenyl (2,4,5 or 6)-
Carboxylic acid, 2,2'-dihalobiphenyl (3,4,5 or 6) -carboxylic acid and alkali metal salts thereof, or the biphenyl group in the above compound is diphenyl ether group, diphenyl sulfone group, diphenyl thioether group, diphenyl methane group , 2,2′-diphenylpropane group, compounds substituted with 1,1,1,3,3,3-hexafluoro-2,2-diphenylpropane group, and the like.

Specific examples of the compound represented by the general formula (IV) include
2,5-dihalonaphthalene-1-carboxylic acid, 2,6-dihalonaphthalene-1-carboxylic acid, 2,7-dihalonaphthalene-1-carboxylic acid, 2,8-dihalonaphthalene-1-carboxylic acid Acid, 3,5-dihalonaphthalene-1-carboxylic acid, 3,6-dihalonaphthalene-
1-carboxylic acid, 3,7-dihalonaphthalene-1-carboxylic acid,
3,8-Dihalonaphthalene, -1-carboxylic acid, 4,6-dihalonaphthalene-1-carboxylic acid, 4,7-dihalonaphthalene-1-carboxylic acid, 4,8-dihalonaphthalene-1- Carboxylic acid, 1,5-dihalonaphthalene-2-carboxylic acid, 1,6-dihalohaphthalene-
2-carboxylic acid, 1,7-dihalonaphthalene-2-carboxylic acid,
3,5-dihalonaphthalene-2-carboxylic acid, 3,6-dihalonaphthalene-2-carboxylic acid, 3,7-dihalonaphthalene-2-carboxylic acid, 3,8-dihalonaphthalene-2-carboxylic acid Acid, 4,6-dihalonaphthalene-2-carboxylic acid, 4,7-dihalonaphthalene-2-
Examples thereof include carboxylic acid, 4,8-dihalonaphthalene-2-carboxylic acid and alkali metal salts thereof.

The two halogen atoms in these halogenoaromatic carboxylic acids and their alkali metal salts are respectively fluorine, chlorine, bromine or iodine, which may be the same or different from each other. Preferable examples of the alkali metal salt include tonalium salt and potassium salt. Further, as the halogenoaromatic carboxylic acid or its alkali metal salt, those in which one or more carboxyl groups or alkali metal salt type carboxyl groups are further introduced at appropriate positions in each of the above compounds are also used. You can

In the method of the present invention, the halogenoaromatic carboxylic acid and its alkali metal salt may be used alone or in combination of two or more, and the carboxyl group contained is a free type, The alkali metal salt type may be used in combination, but the preferable one is
2,4-dichlorobenzoic acid and sodium 2,4-dichlorobenzoate.

In the method of the present invention, a lithium compound is used as a catalyst if desired. Examples of the lithium compound include lithium fluoride, lithium chloride, lithium bromide,
Lithium mineral salts such as lithium iodide, lithium carbonate, lithium hydrogen carbonate, lithium sulfate, lithium hydrogen sulfate, lithium sulfite, lithium phosphate, lithium hydrogen phosphate, lithium dihydrogen phosphate, lithium nitrate and lithium nitrite; chlorine. Lithium oxyacid salts such as lithium oxide, lithium chromate, and lithium molybdate; lithium formate, lithium acetate, lithium oxalate, lithium malonate, lithium propionate, lithium butyrate, lithium isobutyrate,
Lithium maleate, lithium fumarate, lithium 2-methylpropionate, lithium 3-methylbutyrate, lithium valerate, lithium hexanoate, lithium heptanoate, lithium octanoate, lithium tartrate, lithium stearate, lithium benzoate, phthalic acid Lithium carboxylates such as lithium; lithium benzenesulfonate, lithium p-toluenesulfonate such as lithium sulfonates; lithium methoxide, lithium ethoxide, lithium isopropoxide, lithium-n-propoxide, lithium butoxide, lithium Examples thereof include lithium alkoxides such as phenoxide; acetic acid or organic lithium compounds such as lithium acetylacetonate, and various lithium compounds such as lithium sulfide, lithium oxide and lithium hydroxide. Among these, lithium halides such as lithium chloride, lithium carboxylates such as lithium acetate and lithium carbonate are preferable, and lithium acetate and lithium chloride are particularly preferable. These lithium compounds may be used alone or in combination of two or more.

Regarding the use ratio of each raw material component in the method of the present invention, (C) the raw material component dihalogeno-aromatic carboxylic acid or an alkali metal salt thereof is usually 0.01 per mol of the (A) raw material component dihalogeno-aromatic compound. It is used in a proportion of about 1.0 mol, preferably 0.02 to 0.5 mol. If the amount of the raw material component (C) used exceeds the above range, the effect of decreasing the crystallization rate of the copolymer, which is the object of the present invention, cannot be sufficiently exhibited.

In addition, the total amount of the dihalogenoaromatic compound (A) as a raw material component is usually 0.75 to 2.0 mol with respect to 1 mol of the alkali metal sulfide as a raw material component (B),
It is preferably used in a ratio such that it is 0.90 to 1.2 mol.

Furthermore, when a lithium compound catalyst is used, the catalyst is usually used in a proportion of 0.03 to 2.0 mol, preferably 0.1 to 1.6 mol, based on 1 mol of the alkali metal sulfide of the raw material component (B). If the amount of this catalyst is less than 0.03 mol, the molecular weight of the resulting copolymer may be low, or the content of contaminant salts such as sodium chloride present in the copolymer may not be sufficiently low. If it exceeds 2.0 mol, the catalytic effect is not exhibited for the amount, and the catalyst may remain in a high concentration in the produced copolymer, which is not preferable. When lithium sulfide is used as the alkali metal sulfide of the raw material component (B), this can be regarded as a catalyst as well as the raw material component (B).

The amount of the polar solvent used in the method of the present invention is not particularly limited as long as it is an amount sufficient for the reaction to proceed uniformly, and is usually a raw material component of (A), (B) or (C) and It is selected in the range of 0.1 to 10 times the total weight of the catalyst. If this amount is less than 0.1 times by weight, the reaction may be non-uniform, and if it exceeds 10 times by weight, the volume efficiency becomes poor and the productivity is lowered, which is not preferable.

In the method of the present invention, in a polar solvent, in the presence of a lithium compound optionally used, (A) a dihalogenoaromatic compound as a raw material component, (B) an alkali metal sulfide as a raw material component, and (C) a raw material component When the desired arylene sulfide copolymer is produced by contacting the dihalogeno aromatic carboxylic acid or the alkali metal salt thereof with a lithium compound or an alkali metal sulfide, or both are in a water-containing state or a hydrate. First, the lithium compound and an alkali metal sulfide are added to a polar solvent, and dehydration operation such as azeotropic distillation is performed, and these are made substantially anhydrous before preparing a mixed solution. It is preferable that the substantially anhydrous (A) raw material component and (C) raw material component are added to and reacted.

In the method of the present invention, if desired, an active hydrogen-containing halogeno aromatic compound, a polyhalogeno aromatic compound,
A branching agent or molecular weight modifier such as a halogeno aromatic nitro compound, a liquidity modifier such as an alkali hydroxide, a polymerization additive such as a metal salt, a reducing agent, an inert organic solvent, etc. are appropriately selected and reacted. The reaction can be carried out by adding it to the system. It is preferred that these added components are subjected to the reaction in a substantially anhydrous state.

The active hydrogen-containing halogeno aromatic compound is, for example, an amino group, a thiol group, a halogeno aromatic compound having a functional group having an active hydrogen such as a hydroxyl group, such as, for example, 2,6 -Dihaloanilines such as dichloroaniline, 2,5-dichloroaniline, 2,4-dichloroanilene and 2,3-dichloroaniline, 2,
3,4-trichloroaniline, 2,3,5-trichloroaniline,
Trihaloanilines such as 2,3,6-trichloroaniline, 2,4,5-trichloroaniline, 2,4,6-trichloroaniline and 3,4,5-trichloroaniline, 2,3,4,5-tetra Tetrahaloanilines such as chloroaniline and 2,3,5,6-tetrachloroaniline, 2,2'-diamino-4,4'-dichlorodiphenyl ether, 2,4'-diamino-2,4'-dichlorodiphenyl ether And dihalodiaminodiphenyl ethers, and compounds in which an amino group is replaced with a thiol group or a hydroxyl group in these compounds. Further, an active hydrogen-containing halogeno aroma in which a hydrogen atom bonded to a carbon atom forming an aromatic ring in the active hydrogen-containing halogeno aromatic compound is substituted with another inert group such as a hydrocarbon group such as an alkyl group. Group compounds can also be used. Of these various active hydrogen-containing halogeno aromatic compounds, the active hydrogen-containing dihalogeno aromatic compounds are preferable, and dichloroaniline is particularly preferable.

The polyhalogeno aromatic compound is a compound in which three or more halogeno atoms are substituted, and examples thereof include 1,2,4-trichlorobenzene, 1,3,5-trichlorobenzene and 1,4 , 6-trichloronaphthalene and the like.

Examples of the halogeno aromatic nitro compound include mono- or dihalonitrobenzenes such as 2,4-dinitrochlorobenzene and 2,5-dichloronitrobenzene, 2-
Dihalonitrodiphenyl ethers such as nitro-4,4'-dichlorodiphenyl ether, 3,3'-dinitro-4,4 '
-Dihalonitrodiphenyl sulfones such as dichlorodiphenyl sulfone, 2,5-dichloro-3-nitropyridine, 2
Examples include mono- or dihalonitropyridines such as -chloro-3,5-dinitropyridine, and various dihalonitronaphthalenes.

By using these active hydrogen-containing halogeno aromatic compounds, polyhalogeno aromatic compounds, halogeno aromatic nitro compounds, etc., the degree of branching of the copolymer produced can be increased, the molecular weight can be further increased, or the residual content can be increased. Various physical properties of the copolymer can be improved by, for example, lowering the salt.

Further, as the branching agent or the molecular weight adjusting agent, in addition to the above compounds, for example, a compound having three or more reactive halogen atoms such as cyanuric chloride can be used. In the present invention, these branching agents or molecular weight modifiers may be used alone or in combination of two or more.

Examples of the metal salt used as the polymerization additive include carboxylic acid salts of metals belonging to groups I to IV of the periodic table such as sodium acetate, potassium acetate and zinc acetate; alkali metal mineral acids such as sodium phosphate. Examples thereof include salts, alkaline earth metal mineral salts; alkali metal sulfonates such as sodium benzenesulfonate.

These metal salts may be used alone or 2
You may use it in combination of 2 or more types.

Examples of the reducing agent include hydrazine, metal hydride, alkali formate, and the like, and preferable examples include metal hydride, particularly sodium borohydride, calcium hydride, and the like.

Further, examples of the inert solvent include hydrocarbons such as benzene, toluene, xylene, biphenyl, terphenylnaphthalene, and anthracene, ethers such as diphenyl ether, p-diphenoxybenzene, and polyethylene glycol. Of these, high boiling inert organic solvents are preferred.

Next, a preferred example of the embodiment of the present invention will be explained. First, a required amount of a lithium compound used as desired and an alkali metal sulfide of a raw material component (B) are added in a polar solvent, and if necessary, For example, after dehydration operation such as azeotropic distillation, a predetermined amount of (A) a raw material component dihalogenoaromatic compound, (C) a raw material component dihalogenoaromatic carboxylic acid or an alkali metal salt thereof and, if necessary, The various addition components to be used are added, and the polymerization reaction is usually carried out by heating to a temperature in the range of 180 to 330 ° C, preferably 220 to 300 ° C. If this reaction temperature is less than 180 ° C, the reaction rate is too slow to be practical, while if it exceeds 330 ° C, side reactions or deterioration of the produced polymer occur, causing coloring or gelation. The reaction time depends on the type and amount ratio of the raw material components used, the type and amount of the catalyst, the reaction time, etc., and cannot be determined unconditionally, but it is usually within 20 hours, preferably 0.1 to
It is about 8 hours.

This polymerization reaction can be carried out in an atmosphere of an inert gas such as nitrogen, argon, carbon dioxide or water vapor, and the reaction pressure is not particularly limited, but usually the self-pressure of the polymerization reaction system such as a solvent or 50 kg / The reaction is carried out at pressures up to cm ² (absolute pressure).

When the lithium compound and the alkali metal sulfide of the raw material component (B) are both anhydrous, the order of adding the components to the polar solvent is not particularly limited. The reaction may be a one-step reaction conducted at a constant temperature, a multi-step reaction in which the temperature is raised stepwise, or a reaction mode in which the temperature is gradually and continuously raised.

In this way, after the polymerization reaction is completed, the produced copolymer may be directly isolated from the reaction solution by a commonly used method, for example, means such as filtration or centrifugation, or the reaction completed solution. After adding water, diluted acid or the like to the above, it may be isolated by the above method.

Next, the isolated copolymer is usually washed with water, methanol, acetone or the like in order to remove the attached alkali metal halide, alkali metal sulfide, lithium compound and the like. In addition, as described above, without isolating the copolymer produced from the reaction-terminated liquid, the solvent is distilled off, and the obtained residue is washed in the same manner as described above to recover the copolymer. You can also

The arylene sulfide-based copolymer thus obtained can be processed into various molding materials and used, but various desalting treatments may be carried out as necessary to remove sodium chloride in the copolymer. Further reduces the salt content of
It can be suitably used in the electronic field.

When the arylene sulfide-based copolymer obtained by the method of the present invention is molded into various products, the copolymer may include other polymers, pigments, or graphite, metal powder, glass powder, quartz powder, glass. If desired, a filler such as fiber, a stabilizer, a release agent, etc. may be blended and molded.

EFFECTS OF THE INVENTION According to the method of the present invention, a high molecular weight arylene sulfide copolymer having excellent heat resistance, mechanical properties, melt processability, good transparency, and slow crystallization rate can be obtained. It can be easily and efficiently manufactured.

Since the arylene sulfide copolymer has the excellent characteristics as described above, it is preferably used as a material for various molded products, films, fibers, mechanical parts, electric / electronic parts and the like.

[Examples] Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

(Example 1) 1-Autoclave 91.3 g of sodium sulfide pentahydrate
(0.543mol), lithium acetate dihydrate 55.4g (0.543mol)
Then, 297 ml of N-methyl-2-pyrrolidone (NMP) was added, and 160 ml of a water-NMP mixture was distilled off by azeotropic distillation.

Thereafter, 77.4 g (0.526 mol) of P-dichlorobenzene, 3.1 g (0.016 mol) of 2,4-dichlorobenzoic acid and 100 ml of N-methyl-2-pyrrolidone were added, and the mixture was reacted at a temperature of 260 ° C for 3 hours.

After completion of the reaction, the mixture was cooled to 175 ° C. with stirring and left overnight. The reaction mixture was poured into water (1) and filtered, washed with water and washed with acetone in this order. The yield of the obtained polyphenylene sulfide copolymer was 84.7% (50.4 g), and the melt flow value was 0.077 ml / sec.

(Example 2) In Example 1, instead of 3.1 g of 2,4-dichlorobenzoic acid
The same procedure as in Example 1 was carried out except that 3.4 g (0.016 mol) of sodium 2,4-dichlorobenzoate was used.

The yield of the obtained polyphenylene sulfide copolymer is
88.3% (52.8 g) and the melt flow value was 0.069 ml / sec.

(Comparative Example 1) Polyphenylene sulfide was obtained in the same manner as in Example 1 except that 2.4-dichlorobenzoic acid was not used and 79.8 g (0.543 mol) of p-dichlorobenzene was used.

The yield of this polymer was 88.9% (52.2 g) and the melt flow value was 0.0340 mol / sec.

The results are shown in Table 1. The melt flow value is 300
It is a measured value under the conditions of a temperature of 50 ° C., a load of 50 kg / cm ² , and a nozzle length of 10 mm.

Films of the polymers obtained in Examples 1 and 2 and Comparative Example 1 were prepared, and the infrared spectrum was measured by JAPAN SPEC TROSCOPIC C.
When measured by A. of O., LTD, weak absorption was observed near 1720 cm ^{-1 in} Examples 1 and 2, but Comparative Example 1
I didn't see it. This means that the carboxylic acid residue is
It is shown to be present in the polymers of Examples 1 and 2 but not in the polymer of Comparative Example 1.

In addition, in Examples 1 and 2 and Comparative Example 1, the melting peak temperature and the crystal peak temperature were measured by DSC-manufactured by PERKIN-ELMER.
Measured in 2 and analyzed.

The results are shown in Table 1.

(Examples 3 and 4 Comparative Example 2) In Examples 1 and 2 and Comparative Example 1, lithium acetate
The same procedure was performed except that no dihydrate was used.

The results are shown in Table 2.

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Claims (2)

[Claims] 1. A (A) dihalogeno aromatic compound, (B) an alkali metal sulfide, and (C) a dihalogeno aromatic carboxylic acid and / or an alkali metal salt thereof are brought into contact with each other in a polar solvent. A method for producing an arylene sulfide copolymer. 2. A dihalogenoaromatic carboxylic acid and / or its alkali metal salt is 2,4-dichlorobenzoic acid and / or
Alternatively, the production method according to claim 1, which is a sodium salt thereof.